Blue dye and process of making same.



No. 777,323. Patented December 13, 1904.

UNITED STATES PATENT OEEIcE.

JULIUS ABEL,- OF MANNHEIM, AND ARTHUR LUTTRINGHAUS, OF LUD- WIGSHAFEN-ON-THE-RHINE, GERMANY, ASSIG-NORS TO THE BADISOHE ANILIN UND SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE, GER- MANY, A CORPORATION OF BADEN.

BLUE DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent N0. 777,323, dated December 13, 1904:.

Application filed October 24, 1902. Serial No. 128,615. (Specimens) T LI/(Wm it y concern! grade, C.) Maintain this tempera- Be it known that we, JULIUS ABEL, doctor of ture until a test portion of the melt on being philosophy and chemist, a citizen of the free diluted with water neutralized with soda and Hansa town of Hamburg, residing at Mannshaken out with chloroform imparts a violet- 5 heim, in the Grand Duchy of Baden, and Anblue color to the latter without showing any THUR LirrTRINontAUs,cloctor of philosophy and brown red fluorescence, which fluorescence chemist, asubject of the King of Prussia, Emwould be due to the presence of unaltered peror of Germany, residing at Ludwigshafenmethylene violet. On reaching this stage on-the-Rhine, in the Kingdom of Bavaria, Empour the melt onto about four thousand (4, 000) I0 pire of Germany, have invented new and useparts of ice, add ammonia until the liquid ful Improvements in Blue Coloring-Matter shows a faint alkaline reaction, drain on the andProcesses of ProducingSamc, of whichthe pump the coloring-matter which separates following is a specification. out, and wash it well with water and press This invention relates to substantive blue and dry it at ordinary temperature. The col- 5 coloring-matters containing sulfur, which coloringanatter so obtained diflicultly soluble 6o oring-matters directly dye cotton from a bath in chloroform with a blue to blue-Violet color containing sodium sulfid. without fluorescence. It dissolves in concen- We first suitably treat methylene-violet or trated hydrochloric acid, yieldinga pure bluean analogue thereof with sulfur chlorid-for colored solution.

20 instance, that represented by the formula Example 2: 'Into one hundred (100) parts 6 5. S2012. Acoloring-matterherebyresultswhich of crystallized sodium sulfid contained in adirectly dyes cotton blue or blue-violet shades vessel heated, by means of an oil-bath, to about fromabath containing sodium sulfid. We then one hundred degrees centigrade (100 O.) infurther treat this blue-violet coloring-matter troduce thirty (30) parts of the coloring-mat- 5 withsulfur and alkali sullid,whereby coloringter, such as can be obtained according to the matter is obtained which directly dyes cotton foregoing Example 1. When solution of the from a bath containing sodium sulfid shades coloring-matter has been effected, add thirty of blue which are less red than those afore- (30) parts of sulfur to the mixture. Dry the mentioned. mass by gradually raising the temperature of 3 Hereinafter we employ the term methylthe oil-bath to about one hundred and seventy 7 5 ene-violet body to include not only methyldegrees centigrade, (17 09 O.) The mass can one-violet itself, but also its analogues. then, if desired, be directly used for dyeing.

We illustrate methods of carrying out our It is preferred. however, to dissolve it in invention by the following examples (the parts about fifteen hundred (1,500) parts of hot wa- 35 are by weight:) ter and after filtering to precipitate the 001- Example 1: Dissolve during about two (2) oring-niatter (mixed with sulfur) from this hours and at a temperature of about ten desolution by blowing air through it. The colgrees centigrade (10 0.) one hundred oring-matter so obtained is practically insoluparts of methylenewiolet in seven hundred ble in chloroform and concentrated hydro- 4 (700) parts of fuming sulfuric acid, containchloric acid. 5 ing twenty-three (23) per cent. free SO13. Example 3: Into one hundred and twenty Then add to the mixture one hundred (100) parts of molten cystallized sodium sulparts of sulfur chlorid (S2012) and warm the lid heated to about one hundred degrees cen- Whole, While stirring, to a temperature of tigrade (100 O.) and contained in a reflux ap- 45 about from thirty to thirty-five degrees centiparatus introduce'forty (d0) parts of the color- 9 ing-matter, such as can be obtained according to the foregoing Example 1. Then add to the greenish-yellow solution twenty (20) parts of sulfur and boil and stir the whole for from two to four hours (24) or until the initial material has been completely or almost completely converted. When practically no further decrease in the quantity of initial coloring-matter present occurs on shaking out a test portion of the melt after oxidizing with chloroform, the operation is interrupted.

To isolate the new coloring-matter, dilute the melt with from fifteen hundred to two thousand (1,500-2,000) parts of boiling water and filter the diluted melt from any undissolved matter which may be present and blow air through the filtrate. The new coloringmatter mixed with sulfur is thereby precipitated and can be collected in the usual manner.

We claim 1. The process of manufacturing bluish substantive coloring-matter by treating a methylene-violet body, with sulfur chlorid and then subjecting the resulting product to the action of sulfur and alkali sulfid.

2. The process of manufacturing bluish to violet-bluish substantive coloring-matter by treating a methyleneviolet body, with sulfur chlorid.

3. Coloring-matter which can be obtained from a methylene -violet body and sulfur chlorid, which dyes unmordanted cotton from a bath containing sodium sulfid shades which lie within the range of blue to blue-violet, and which coloring-matter is diflicultly soluble in chloroform yielding a blue to blue-violet color and gives a blue-colored solution with concentrated hydrochloric acid.

4. Coloring-matter which can be obtained from a methylene-violet body, sulfur chlorid, sodium sulfid and sulfur, which dyes unmordanted cotton from a bath containing sodium sulfid shades which lie within the range of blue to blue-violet-and which coloring-matter is practically insoluble in chloroform and in concentrated hydrochloric acid.

In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

JULIUS ABEL. ARTHUR LUTTRINGHAUS.

Witnesses:

ERNEST F. EHRHARDT, JACOB ADRIAN. 

